Calculations Predict That Heavy-Atom Tunneling Dominates Mobius Bond Shifting in [12]- and [16]Annulene

被引：6

作者：

Arbitman, Jessica K. ^{[1
]}

Michel, Cameron S. ^{[1
]}

Castro, Claire ^{[1
]}

Karney, William L. ^{[1
]}

机构：

[1] Univ San Francisco, Dept Chem, 2130 Fulton St, San Francisco, CA 94117 USA

来源：

ORGANIC LETTERS | 2019年 / 21卷 / 21期

基金：

美国国家科学基金会;

关键词：

REARRANGEMENT; CYCLIZATION;

D O I：

10.1021/acs.orglett.9b03185

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The contribution of heavy-atom tunneling to reactions of [12]- and [16]annulene was probed using small-curvature tunneling rate calculations. At the CCSD(T)/cc-pVDZ//M06-2X/cc-pVDZ level, tunneling is predicted to account for more than 50% of the rate for Mobius bond shifting and ca. 35% of the rate for electrocyclization in [12]annulene, and over 80% of the rate for Mobius bond shifting in [16]annulene, at temperatures at which these reactions have been observed experimentally.

引用

页码：8587 / 8591

页数：5

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